Nanographenes (NGs) of unique shape, size and properties are always at the center of attraction because of their potential application as semiconducting materials in organo-electronic devices. Contorted NGs have gained increased attention because of their fascinating molecular packing, reduced π-π interaction, enhanced solubility and lower band gap compared to the planar analogues. We have synthesized a library of contorted NGs by utilizing the non-oxidative, alkyne benzannu-lation reaction catalyzed by indium chloride and silver bis triflimide by exploiting high energy content of carbon-carbon triple bonds of the diyne precursors under a mild-reaction conditions. We employed two-fold InCl3/AgNTf2-catalyzed alkyne benzannulation reaction to afford a broad collection of highly functionalized, laterally π-expanded, helicene-like naphtho[1,2-a]pyrene derivatives in moderate to very good yields. We were able to utilize this method to expand conju-gation of the HBC core to get a variety of π-extended HBC NGs. The Suzuki cross-coupling of the halogen(s) substituted smaller polycyclic aromatic hydrocarbons with diyne boronic ester gave polyalkyne precursors, which were subjected to multi-fold alkyne benzannulation reaction to af-ford larger, highly soluble contorted NGs. This work also proved the applicability InCl3 and AgNTf2 in the synthesis of up to six benzene ring in one-pot reaction condition. In most of the cases, the chiral, helically twisted skeletons were unambiguously determined through X-ray crys-tallography. We are also very close (two-steps away) towards the synthesis of longer pyrenacenes such as quateropyrene and quinteropyrene following our previous protocol for the synthesis of pyrene, peropyrene and teropyrene.
|Advisor:||Chalifoux, Wesley A.|
|Commitee:||Sheridan, Robert S., Casey, Sean M., Pinsky, Mark, Sengupta, Shamik|
|School:||University of Nevada, Reno|
|School Location:||United States -- Nevada|
|Source:||DAI-B 81/12(E), Dissertation Abstracts International|
|Subjects:||Chemistry, Organic chemistry, Materials science|
|Keywords:||Alkyne benzannulation reaction, Carbon rich material, Helical NGs, HBC NGs, Lewis acid, Nanographenes, Twisted Nanographenes|
Copyright in each Dissertation and Thesis is retained by the author. All Rights Reserved
The supplemental file or files you are about to download were provided to ProQuest by the author as part of a
dissertation or thesis. The supplemental files are provided "AS IS" without warranty. ProQuest is not responsible for the
content, format or impact on the supplemental file(s) on our system. in some cases, the file type may be unknown or
may be a .exe file. We recommend caution as you open such files.
Copyright of the original materials contained in the supplemental file is retained by the author and your access to the
supplemental files is subject to the ProQuest Terms and Conditions of use.
Depending on the size of the file(s) you are downloading, the system may take some time to download them. Please be